EP0502128A4 - Monomeres a polarisation anionique, leurs polymeres et emploi desdits polymeres dans des agents de reserve. - Google Patents

Monomeres a polarisation anionique, leurs polymeres et emploi desdits polymeres dans des agents de reserve.

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Publication number
EP0502128A4
EP0502128A4 EP19910902819 EP91902819A EP0502128A4 EP 0502128 A4 EP0502128 A4 EP 0502128A4 EP 19910902819 EP19910902819 EP 19910902819 EP 91902819 A EP91902819 A EP 91902819A EP 0502128 A4 EP0502128 A4 EP 0502128A4
Authority
EP
European Patent Office
Prior art keywords
monomer
group
monomers
substrate
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19910902819
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German (de)
English (en)
Other versions
EP0502128A1 (fr
EP0502128B1 (fr
Inventor
John G Woods
Pauline Coakley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Loctite Corp
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Henkel Loctite Corp
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Publication date
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Publication of EP0502128A1 publication Critical patent/EP0502128A1/fr
Application granted granted Critical
Publication of EP0502128B1 publication Critical patent/EP0502128B1/fr
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

  • This invention relates to anionically polymerizable monomers containing at least one silicon or titanium atom, polymers thereof, and use of such polymers in photoresists, particularly for the microelectronics industry.
  • this invention also relates to vapour deposition and polymerization of si1 icon-functionalised cyanoacrylates.
  • anionically (or zwitterionically) polymerisable monomers as resist materials for micro! ithography is known in the art, as discussed in U.S. Patent 4,675,273 Woods et al. and 4,675,270 Woods et. al. both assigned to Loctite (Ireland) Limited, the contents of which are incorporated herein by reference.
  • Such resist materials are usually applied to or formed as a coating on an etchable substrate; the coated substrate is then imaged using high energy radiation; the image is developed by a development process, normally using a solvent; and the image is etched using a suitable plasma or chemical etching process.
  • Chemical etching has a significant disadvantage in that it is isotropic, i.e. the etching can affect the substrate below the photoresist.
  • anistropic etching it is preferred to use dry etching by radio frequency glow discharge or large area ion beam methods. The most preferred methods are: _9_
  • plasma etching e.g. using oxygen or a halocarbon, particularly a fluorocarbon such as CF. or CHdirectorF 7 with chlorine or argon; or
  • the cationic sensitive monomer may be an organo etal 1 ic monomer wherein the organometal 1 ic elements include silicon, germanium and tin.
  • Particular examples of monomers include an epoxy substituted siloxane or silane or a silyl substituted vinyl ether.
  • the monomer may be dissolved in a solvent or may be in the vapor state.
  • the present invention provides anionically polymerizable monomers of the formula I
  • X is a strong electron withdrawing group;
  • Y is a strong electron withdrawing group containing at least one silicon cr titanium atom.
  • strong electron withdrawing group refers to groups which are more electron withdrawing than halo.
  • X may suitably be selected from -CN, -COR, -C00R, -SO-R and -S0-.R wherein R is H or a hydrocarbyl group, preferably a C,-C, ? hydrocarbyl group.
  • R is H or a hydrocarbyl group, preferably a C,-C, ? hydrocarbyl group.
  • X is -CN.
  • Y may suitably be selected from -COR , -C00R , -S0 R and
  • R is a group containing Si or Ti, preferably a hydrocarbyl, aryl or hydrocarbylaryl group (or a substituted derivative thereof) substituted with a group containing Si or Ti.
  • hydrocarbyl as used herein means "aliphatic hydrocarbyl” including alkyl, alkenyl and alkynyl. Hydrocarbyl groups shall preferably contain from 1 to 10 carbon atoms, more preferably from 1 to 5 carbon atoms, and aryl and hydrocarbylaryl groups shall preferably have from 6 to 20 carbon atoms, more preferably from 6 to 10 carbon atoms. Hydrocarbyl groups are preferred, especially alkyl or alkenyl groups. A substituted derivative of the foregoing may suitably be substituted with one or more halo or alkoxy groups or interrupted by one or more oxygen or nitrogen atoms. Halogen may be chlorine, bromine, fluorine or iodine.
  • the groups ' for R are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, a hexyl group, an allyl group, a methallyl group, a crotyl group, a propargyl group, a cyclohexyl group, a benzyl group, a phenyl group, a phenoxide group, a cresyl group, a 2-phenylethyl group, a 2-chloroethyl group, a 3-chloropropyl group, a 2-chlorobutyl group, a trifluoroethyl group, a 2-methoxyethyl group, a 3-methoxybutyl group or a 2-ethoxyethyl group, substituted with a group containing Si or Ti.
  • R comprises or is substituted with at least one group consisting of or containing R 3 1 . 2 -Si-R
  • R 2 3 4 selected from H (provided that not more than one of R , R_ and R is H), C,-C, 0 alkyl, aryl, C,-C, Q alkoxy and siloxy groups of the formula:
  • R , R and R which may be the same or different are selected from H, CH-, or phenyl, provided that not more than one of R 5 , R 6 and R 7 is H;
  • R may also be a group selected from siloxane oligomers or polymers of the structure
  • R , R and R are defined as above and is an integer from 2 to 100.
  • ' m is in the range from 2 to 20, and most preferably in the range from 2 to 5.
  • m be low, for example not more than 2.
  • Alkyl groups shall preferably contain 1 to 5 carbon atoms and aryl groups shall preferably have from 6 to 10 carbon atoms, most preferably being phenyl.
  • Y is -C00(CH 2 ) n -Si-fr
  • n 1-5 and R , R and R are as defined above.
  • n is at least 3.
  • R , R J and R are
  • a particularly preferred monomer is 3-trimethylsilylpropyl 2-cyanoacrylate of the formula II
  • the present invention also provides polymers formed by anionic polymerization of monomers of Formula I as described above.
  • the invention provides polymeric photoresists formed by polymerisation of monomers of Formula I.
  • the photoresists are preferably formed by polymerization from monomer vapour to produce a polymeric film on a substrate, in the manner described in U.S. Patent 4,675,273 or 4,675,270.
  • the invention provides a method for applying a polymeric resist coating to a substrate which comprises exposing the substrate to the vapour of a monomer of formula I as defined in Claim 1 for sufficient time to deposit a polymerized coating of the monomer on the substrate.
  • the substrate has a planarizing layer of etchable polymeric material applied thereto before the resist coating of the monomer of formula I is deposited thereon.
  • the monomer may be polymerized in solution or in the bulk state and deposited on the substrate e.g. by spin coating to form a photoresist.
  • Photoresist films produced from monomers of Formula I may be processed similarly to conventional polycyanoacrylates, but they have significantly improved dry etch resistance as compared to photoresists formed of conventional polycyanoacrylates. They also have improved dry etch resistance as compared to other conventional photoresist materials exemplified by poly(methylmethacrylate) and Novolac systems.
  • Photoresist films produced from monomers of Formula I have been found to normally image with negative tone, in contrast with photo ⁇ resists formed from conventional poly(cyanoacrylates) which image with positive tone.
  • negative tone is meant that upon exposure to UV radiation through a mask followed by solvent treatment, the unexposed areas are dissolved away, whereas by “positive tone” is meant that on similar treatment the exposed areas are removed by the solvent.
  • the monomers of Formula I may be used to form photoresists with positive tone images by coating the substrate with a compound which releases acid upon irradiation, image-wise exposing the coated substrate, and then forming the photoresist by deposition from monomer vapour, as described in U.S. Patent 4,675,270 for poly ⁇ cyanoacrylates).
  • a polymer is prepared and then dissolved in a suitable solv.it such as dichloromethane, acetone, nitro ethane, tetrahydrofuran, acetonitrile, or chloroform.
  • a suitable solv.it such as dichloromethane, acetone, nitro ethane, tetrahydrofuran, acetonitrile, or chloroform.
  • the monomer vapours may be generated from the monomers at ambient temperatures and pressures but it is generally preferred to heat the monomers and/or reduce the atmospheric pressure above the monomer generated in the chamber in order to generate sufficient concentrations of vapour to accomplish the polymer deposition on the substrate in a reasonable time.
  • any substrate upon which a polymeric image is desired may be utilized in the inventive processes.
  • the substrates will be ones which undergo subsequent plasma etching during which the polymer coating serves as an etch resist.
  • Suitable substrate materials include silicon dioxide, including SiO- coated silicon, metallic oxides, and glass, all of which may be etched by plasma etching processes.
  • the preferred substrate is SiO ? coated silicon, e.g. the silicon chips conventionally used in preparation of semi-conductor devices. Most suitably, this substrate is etched by plasma etching process.
  • a planarizing layer of etchable polymeric material such as poly(methylmethacrylate) may be applied to the substrate before the resist layer is applied thereon.
  • Suitable activators include the known initiators for anionic or zwitterionic polymerization of alky! cyanoacrylates. Especially suitable activators are organic amines and phosphines.
  • a conventional solvent development process may be used to develop the image, e.g. immersion in ethyl acetate, isobutyl methyl ketone, acetone or blends of ethyl acetate with either of isobutyl methyl ketone and acetone.
  • Compounds which release acid upon irradiation for the process of forming a positive tone photoresist include any compounds which release Lewis or proto ⁇ ic acids such as those known as photoinitiators for cationically polymerizable resins such as epoxies or vinyl ethers.
  • Suitable radiation sensitive acid precursors useful in the inventive method include salts of complex halogenides represented by the formula
  • A is a cation selected from iodonium, iodosyl, Group Via onium, pyryliu , thiopyryl ium, sulfonylsulfoxonium, and diazoniu
  • M is a metal or metalloid
  • X is a halogen radical
  • d e-f
  • f the valence of M and is an integer equal to from 2 to 7 inclusive and e is greater than f .and is an integer having a value up to 8;
  • R 8 [0.S0 2 -CQ 3 ] n , o
  • R is an organic radical of valency 1 to 4 and Q is hydrogen or fluorine ar.
  • ⁇ ' is an integer from 1 to 4; and compounds which release sulfonic acids when irradiated such as those disclosed in U.S. Patent Nos. 4,504,372 and 4,510,290, both incorporated herein by reference.
  • the acid generating compound may be applied neat or in a solvent which is subsequently evaporated. If a surface activator is also to be applied to the substrate, both the activator and the acid generating compound may be applied simultaneously in a common solvent. Alternatively, the activator may be applied before or after application of the acid generating compound.
  • Mirror finish substrates may be repolished, e.g. with a suitable tissue, after application of these compounds and still retain sufficient activator and acid generator to give sharply imaged resists after irradiation and exposure to monomer vapour.
  • Figure 1 is a graph showing vapour deposition growth rates of 3-trimethylsilanpropyl 2-cyanoacrylate as described in Example 3
  • Figure 2 is a schematic diagram of a multilayer photoresist system
  • Figure 3 is a schematic diagram of selective deposition of monomer on an inhibitor-imaged substrate
  • Sheets 4-6 set out formulae of exemplary monomers for use in the invention.
  • 3-trimethylsilylpropyl 2-cyanoacetate (31.84g, 0.16 moles) prepared as described in Example 1, was added dropwise over 10 minutes to a stirred solution of paraformaldehyde (4.8g, 0.16 moles formaldehyde) and piperidine (0.12g) in n-butylacetate at 70°C.
  • paraformaldehyde 4.8g, 0.16 moles formaldehyde
  • piperidine 0.12g
  • the mixture was heated under reflux in a Dean-Stark apparatus until the quantitative amount of water expected from formaldehyde condensation had been collected (2.8g).
  • the mixture was allowed to cool and phosphorous pentoxide (0.57g), p_-toluenes ⁇ lfonic acid (1.09g) and 1 ,4-hydroquinone (2.18g) were added.
  • Photoresist layers of poly were prepared by a vapour phase deposition process of the corresponding monomer, prepared as described in Example 2, according to the following proceedure .
  • a polished silicon wafer three inches in diameter was activated by pouring a sufficient quantity of a solution of 10% N , N . N , N-tetramethylethylenediamine ( TMED ) in 1 , 1 , 1 , 3,3, 3-hexamethyldisiIazane ( HMDS ) to cover the surface.
  • TMED N-tetramethylethylenediamine
  • HMDS 3-hexamethyldisiIazane
  • the corresponding film thickness may be calculated according to the relationshi p:
  • a silicon wafer, 3 inches in diameter was vapour coated with 2. 1 milligrams ( 0.46 ⁇ m ) of poly ( 3-trimethylsilyl propyl 2-cyanoacrylate ) by the procedure described in Example 3.
  • the coated wafer was then imagewise exposed to ultraviolet ( UV ) light from a medium pressure mercury arc lamp (operating at 80 Wcm ) through a 4 inch ( 10 cm) square chrom plated quartz test mask which had alternate opaque and transmissive elements of varying sizes over the range 1000 - 1 micrometers patterned on the surface.
  • a copper plate 4 inches ( 10 cm ) square and 5/8 inches ( 1 .6cm ) in thickness with a 2 inch ( 5cm ) square centralized hole was placed on the perimeter of the mask .
  • the weight of the copper plate was 1 kilogram .
  • the coated wafer, mask and copper plate assembly was located directly below the arc lamp such that the distance between the arc and wafer was 20 cms .
  • the wafer was exposed to UV light for 120 seconds , cooled to room temperature and immersed for 30 sees , in a bath of developer solvent, prepared by blending one part of toluene with 4 parts of petroleum spirit b . p . 40-60°C .
  • a silicon wafer, 3 inches in diameter was vapour coated with 3.55 milligrams (0.78 ⁇ m) of poly(3-trimethylsilyl propyl 2-cyanoacrylate) by the method described in Example 3.
  • the coated wafer was scribed and broken in small pieces approximately 10 x 10mm 2 in size.
  • the small wafers were mounted in. a scanning electron microscope and exposed to an electron beam,0.1 ⁇ m in diameter, at an accelerating voltage of 25 KV for varying current beam densities (radiation dose) over the range 41-205 ⁇ C.cm .
  • a ⁇ eries of 8 lines 10, 5, 2, 1, 0.8, 0.6, 0.4 and 0.3 ⁇ m were irradiated in a vector scan mode. Following irradiation, the wafers were developed by immersion in a bath of a toluene/petroleum spirit blend (4:96) for 60 se s. followed by rinsing with isopropyl alcohol for 60 sees.
  • a silicon wafer approximately ' 1 cm 2 was vapour coated with 0.8 ⁇ m of poly (3-trimethylsilylpropyl 2-cyanoacrylate) (PTSCA) according to the proceedur described in Examples 3 and 5.
  • the resist coated wafer was placed in a plasma reactor along with a similar substrate which had been sputter coated with I.O ⁇ m of silicon dioxide (SiO-) and exposed to a plasma of argon and trifluoromethane (Ar/CHF 3 ) under reactive ion etching conditions at 120 watts for sufficient time to allow the etching rates to be determined.
  • PTSCA poly (3-trimethylsilylpropyl 2-cyanoacrylate)
  • PECA polyl ethyl 2-cyanoacrylate
  • the etch rate of PTSCA resist in an oxygen plasma was also determined in a related experiment.
  • the etch resistance was compared not only to PECA but also to a number of commercially available photoresist products. The results obtained are, as follows: o . Relative Etch
  • the experiment shows that the silicon containing PTSCA is over 30 times more resistant to 0 2 plasma than non silicon containing PECA resist and approximately 15 times more resistant to a number of popular commercial products.
  • Examples 4-6 demonstrate the utility of the new polymer as a solvent developed, negative acting, single layer photoresist having outstanding resist to plasma etching.
  • the polymer is, however, also suitable as an imaging mas layer in a multilayer photoresist system .
  • Multilayer resists are usually designed to separate the imaging function of a photoresist from its planarizin function and the technique is particularly useful where relief images over stepped features are required .
  • a typical multilayer photoresist consists of an underlying relatively thick ( 1 -5 ⁇ m) planarizing layer over which a thin imaging layer (0.1-0.3 ⁇ m) is deposited .
  • the polymeric materials of the present development are particularly suitable for use as the thin imaging layer of multilayer resist system and function as a plasma or DUV contact mask ensuring image transfer through the planarizing layer to the substrate surface.
  • the first step involves the application of a relatively thick planarizing layer which may consist of any 0 2 plasma or DUV sensitive polymeric material suc as poly(methylmethacrylate ) ( PMMA ) .
  • the polymer is applied by conv ntiona means for example by spin casting from solution onto a substrate and baking to remove solvent.
  • the polymeric solution may optionally contain a small quantity of a non-volatile anionic polymerization initiator such as an amine or phosphine ( e. g . 0.01% piperonylamine ) .
  • a non-volatile anionic polymerization initiator such as an amine or phosphine ( e. g . 0.01% piperonylamine ) .
  • the surface of the dr polymer may be activated by a short exposure to vapour of a volatile amine (e.g . 2 mins.
  • the planarizing layer is next exposed to monomer 3-trimethylsilyl - propyl 2-cyanoacrylate and the imaging layer is grown (typically 0. 1 -0.3 ⁇ m film thickness ) .
  • the preferred method of growth is by the vapour depositio procedure as outlined in Example 3 although the polymer may also be grown by immersion of the substrate in a solution of the monomer dissolved in a suitable solvent ( e.g . two minutes immersion in 5% solution in petroleum spirit ) or by spin casting from solution .
  • the bi-layer photoresist is then imagewise exposed to UV light and the imag developed as described in Example 4.
  • the photoresist is then exposed to a oxygen plasma for sufficient time to etch the planarizing layer and expose the substrate. Since the plasma etches anisotropically. relief images with excellent aspect ratios are achieved particularly over stepped features .
  • the imaged bi-layer resist may be flood exposed to DUV irradiation and the planarizing layer developed by means of a suitable solvent.
  • a layer of a photosensitive latent acid catalyst i. e. a material capable of producing strong acid on exposure to radiation ! directly onto the substrate .
  • a layer of a photosensitive latent acid catalyst i. e. a material capable of producing strong acid on exposure to radiation ! directly onto the substrate .
  • This may preferably be a modified planarizing layer ( e . g . 4 ⁇ m PMMA ) or alternatively may be placed directly over a planarising layer .
  • the layer is conveniently referred to as an inhibitor layer ( e .g . 0. 2 ⁇ m film of poly ( 4-methoxystyrene ) containing 20% by weight of CE 1014, a commercially available latent acid catalyst supplied by General Electric Corp. ) .
  • the layer ( s ) are deposited by conventional spin coating methods and preferably contain a small quantity of cyanoacrylate polymeri zation initiator.
  • Useful latent acid catalysts include triarylsulfonium and diaryiiodonium salts containing non-nucleophilic counterion and benzene sulfonate esters of ben zoin and should account for between one and 30% of the dry polymer weight . Irradiation of the layer ! s ) through a mas at wavelengths corresponding to the absorption characteristics of the latent acid, produces a pattern of strong acid in the inhibitor layer which correspon to a positive image of the mask pattern .
  • the patterned resist is next exposed to monomer 3-trimethylsilyl propyl 2-cyanoacrylate. preferably by vapour deposition as described in Example 3 although solution methods may also be used to selectively grow the correspond polymer on the- unexposed regions of the inhibitor or photosensitive layer- Polymer does not grow on the exposed areas where the photo- generated strong acid inhibits the anionic polymeri zation of the monomer .
  • I t i important to ensure that concentration of photogenerated acid exceeds the concentration of anionic polymeri zation initiator inc luded in the planarizatio ⁇ o inhibitor layers .
  • a positive tone relief image of the mask is transferred into the photosensitive/ inhibitor layer without the need for a solvent developm step .
  • the imaged resist is next exposed to an oxygen plasma for sufficient time to transfer the image through the photosensitive/inhibitor and planarizing layer ( if present) to expose the substrate.
  • This step may be preceded by flood exposing the coated wafer to DUV light to alter the solution characteri stics of the pl asma mask.
  • the image may be transferred by first flood exposure to DUV light and developing the image in a suitable solvent.
  • the process is shown schematically in Fig . 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Dental Preparations (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials For Photolithography (AREA)
EP91902819A 1989-11-21 1990-11-20 Monomeres a polarisation anionique, leurs polymeres et emploi desdits polymeres dans des agents de reserve Expired - Lifetime EP0502128B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
IE371389 1989-11-21
IE371389 1989-11-21
US54246490A 1990-06-22 1990-06-22
US542464 1990-06-22
PCT/US1990/006832 WO1991007446A1 (fr) 1989-11-21 1990-11-20 Monomeres a polarisation anionique, leurs polymeres et emploi desdits polymeres dans des agents de reserve

Publications (3)

Publication Number Publication Date
EP0502128A4 true EP0502128A4 (fr) 1992-04-02
EP0502128A1 EP0502128A1 (fr) 1992-09-09
EP0502128B1 EP0502128B1 (fr) 1996-01-03

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EP91902819A Expired - Lifetime EP0502128B1 (fr) 1989-11-21 1990-11-20 Monomeres a polarisation anionique, leurs polymeres et emploi desdits polymeres dans des agents de reserve

Country Status (8)

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US (1) US5359101A (fr)
EP (1) EP0502128B1 (fr)
JP (1) JPH05504366A (fr)
AT (1) ATE132510T1 (fr)
CA (1) CA2019669A1 (fr)
DE (1) DE69024661T2 (fr)
ES (1) ES2082191T3 (fr)
WO (1) WO1991007446A1 (fr)

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US5359101A (en) 1994-10-25
DE69024661D1 (de) 1996-02-15
HK1005457A1 (en) 1999-01-08
DE69024661T2 (de) 1996-08-01
ATE132510T1 (de) 1996-01-15
EP0502128A1 (fr) 1992-09-09
WO1991007446A1 (fr) 1991-05-30
ES2082191T3 (es) 1996-03-16
CA2019669A1 (fr) 1991-05-21
JPH05504366A (ja) 1993-07-08
EP0502128B1 (fr) 1996-01-03

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